Lead-provided porous metal sheet and method for manufacturing the sheet

ABSTRACT

A method of manufacturing a lead-provided porous metal sheet comprises the steps of: forming a porous metal material having a metal layer on a surface of a framework of a porous base material comprising a foamed sheet and the like, by plating the porous base material and/or applying fine metal powders thereto; passing the porous metal material through a pair of rolls having a plurality of projections formed thereon to compress the porous metal material against the projections and reduce or eliminate pores so as to form one or more recesses extending; and forming solid metal portions by applying fine metal powders to the entire recesses.

This is a divisional of application Ser. No. 08/352,613 filed Dec. 9,1994 now U.S. Pat. No. 5,508,114.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a lead-provided porous metal sheet anda method for manufacturing the same, and more particularly, to alead-provided porous metal sheet preferably used as a spiral typeelectrode plate of a battery. In order to use, as a spiral typeelectrode plate, a porous metal sheet formed by using a combination ofporous sheets such as a foamed sheet, a piece of nonwoven cloth, and amesh sheet or only one of these three types of sheets, an activesubstance into pores of the porous metal sheet. In this manner, leadsconsisting of continuous solid metal serving as a collection element forcollecting electric current is formed along the peripheral edge of thespiral type electrode.

2. Description of the Related Art

In the case of a cylindrical battery having the spiral type electrodeplate, the porous metal sheet is used as the core of both positive andnegative electrode plate. The band-shaped positive and negativeelectrode plates formed by charging the active substance into pores ofthe porous metal sheet are spirally wound, with a separator interposedtherebetween.

In order for the battery having the spiral type electrode plate tocollect electric current, and one end of a collection terminal isconnected with a portion of the positive and negative electrode platesby spot welding, respectively and the other end of the collectionterminal welded to the positive electrode plate is welded to a sealingportion, provided with a cap, serving as a positive terminal, and otherend of the collection terminal welded to the negative electrode plate iswelded to the inner bottom surface of the metal casing of the battery.

In the case where each collection terminal is connected with eachelectrode plate at one point thereof by spot welding, the distancebetween the point at which electric current has been generated in theelectrode and each collection terminal is long and further, collectedelectric current flows only through one collection terminal.Consequently, the internal resistance of the battery is great.

Because the rigidity of the porous metal sheet becomes very high whenthe active substance is charged into pores thereof, there is a highpossibility that the porous metal sheet is broken when it is woundspirally. If the lead is not broken, electric current can be collectedeffectively, while if the lead is broken, the porous metal sheet cannotfunction.

Thus, as shown in FIG. 13, a battery of multipoint collection type isproposed: A positive electrode plate 1 and a negative electrode plate 2are spirally wound by varying the vertical position of the positiveelectrode plate 1 and that of the negative electrode 2 a little fromeach other, with a separator interposed therebetween; an upper edgeportion of electrodes 1 and a lower edge portion of electrodes 2 areproject respectively upward and downward from a core portion piled withelectrodes 1 and 2; leads 4 and 5 made of solid metal are provided onthe projected portion of the electrodes; collection terminals 6 and 7made of metallic lath plate, a metallic net, or a metallic plate areplaced on the leads 4 and 5, respectively, and the collection terminals6 and 7 are welded to each of the leads 4 and 5. There is a case wherethe collection terminals 6 and 7 are connected with each of the leads 4and 5 at one point thereof.

Methods shown in FIGS. 14A and 14B are known as the method for formingthe electrode plates 1 and 2 having the leads 4 and 5 provided at oneend thereof.

According to the method shown in FIG. 14A, initially, a porous metalsheet 10 is pressed in the widthwise direction thereof at regularintervals to form lead portions 10a having very small percentage ofpores. Then, an active substance is charged into pores of the porousmetal sheet 10. At this time, the active substance is not charged intothe lead portions 10a because the lead portions 10a have very smallpercentage of pores. Then, the porous metal sheet 10 is slitted alongthe lead portions 10a in the lengthwise direction thereof. Then, theporous metal sheet 10 is cut in directions perpendicular to thelengthwise direction thereof to a length necessary to be used in abattery. Thereafter, a lead plate 10b made of a narrow band-shaped metalplate is welded to each of the lead portions 10a because the leadportions 10a are thin and hence does not have a high strength. In thismanner, leads 4 and 5 are formed.

According to the method shown in FIG. 14B, first, lead plates 10b madeof a narrow band-shaped metal plate are welded to the porous metal sheet10 by spacing the lead plates 10b at regular intervals in the widthwisedirection of the porous metal sheet 10 to form the leads 4 and 5. Then,an active substance is charged into pores of the porous metal sheet 10.At this time, the active substance is not charged into the leads 4 and 5because the lead plates 10b have been welded to the porous metal sheet10. Then, the porous metal sheet 10 is slitted and cut to form anelectrode plate to be used in a battery.

In the above-described electrode plate, the narrow band-shaped metalplate 10b is welded to the porous metal sheet to form the leads thereon.The metal plate 10b is very thin and the width thereof is as small as1.0 mm-5.0 mm. Thus, it is very difficult to weld the metal plate 10b tothe porous metal sheet 10 and further, welding positions are frequentlydislocated from predetermined welding positions.

In order to overcome the above-described disadvantage, the presentapplicant proposed the electrode plate having leads (disclosed inJapanese Laid-Open Patent Publication No. 3-241662). The electrode plateis made of a porous metal sheet formed by plating a combination ofthree-dimensional net-shaped porous sheets such as a foamed sheet, apiece of nonwoven cloth, and a porous mesh sheet layered one on theother or only one of the above three types of porous sheets which can beallowed to have porosity at more than 90%.

According to the method for forming leads on the three-dimensionalnet-shaped porous metal sheet, a lead-forming sheet is overlaid on thesurface of a combination of porous sheets such as the foamed sheet, thenonwoven cloth, and the mesh sheet layered one on the other or only oneof them, and then, plating is performed. As a result, the leadsconsisting of solid metal are continuously formed.

The above-described three-dimensional net-shaped porous metal sheet hasporosity at more than 90% and eliminates the process of welding themetal plate forming a lead to the porous metal sheet. But it isnecessary to layer the lead-forming sheet on the base sheet in platingthe base sheet. Thus, it takes much time and labor to mount lead-formingsheet on the base sheet.

In addition, it is necessary to prepare a lead-forming sheet consistingof a metal foil sheet or a resin sheet having tape-shaped lead-formingportions continuously formed at regular intervals and the porousportions interposed between the lead-forming portions; a metal foiltape; a water-soluble film having the lead-forming portions printed withcoating material, resin or metal powders; a lead-forming sheet havingfine meshes in lead-forming portions and having a porosity at 40-90%,provided in portions between the lead-forming portions. Thus, the costfor manufacturing the lead forming sheet is high and takes much time andlabor.

Further, in order to form the lead by plating, a masking sheet on whichmetal is not deposited is adhered to portions of the surface of theporous metal sheet formed by a primary plating except for thelead-forming portions thereof, when the lead is formed by plating. Inaddition, another masking sheet is required in forming a wide lead by asecondary plating. Thus, it takes much time and labor to install themasking sheet on the porous metal material and remove it therefrom.

Furthermore, it is necessary to provide another lead-forming sheet inaltering the width of the lead or the interval between the leads.

SUMMARY OF THE INVENTION

The present invention has been developed with a view to substantiallysolving the above described disadvantages and has for its essentialobject to provide an improved porous metal sheet having leads,consisting of solid metal, which can be formed very easily in formingthe porous metal sheet from a three-dimensional net-shaped base materialand a method for manufacturing the lead-provided porous metal sheet.

In order to achieve the aforementioned object, a method of manufacturinga lead-provided porous metal sheet comprises the steps of:

forming a porous metal sheet having a metal layer formed on a surface ofa framework of a porous base material comprising a foamed sheet, a pieceof nonwoven cloth or a mesh sheet or a combination of two or more of thefoamed sheet, the nonwoven cloth, and the mesh sheet layered one on theother, by plating the porous base material and/or applying fine metalpowders thereto;

passing the porous metal sheet through a pair of rolls having aplurality of projections formed thereon to compress the porous metalsheet against the projections and reduce or eliminate pores so as toform one or more recesses extending continuously in the lengthwisedirection of the porous metal sheet by spacing the recesses at regularintervals in the widthwise direction thereof; and

forming solid metal portions by applying fine metal powders to theentire recesses;

whereby at least one lead made of the solid metal is formed thereoncontinuously in a predetermined width on the porous metal sheet.

When the porous metal sheet having a thickness of 1.6 mm and a porosityof 95% is passed through a pair of rolls having projections to reducethe thickness thereof to 0.08 mm at the recess, the porosity of therecess becomes 0%. When the thickness of the porous metal sheet isreduced to 0.2 mm, the porosity of the recess is reduced to 60%. Thus,when fine metal powders are applied to the recess, solid metal having nopores can be formed.

A pair of rolls having the projections are disposed on upper and lowersides of the base sheet to form recesses on the upper and lower surfacesthereof. Then, fine metal powders are applied to the recesses, and then,pressed by the upper and lower projections of the rolls so as to formthe solid metal portions on the upper and lower surfaces of the basesheet. Needless to say, the solid metal portions may be formed on one ofthe upper and lower surfaces of the base sheet.

In another aspect of the present invention, a method of manufacturing alead-provided porous metal sheet comprises the steps of:

forming the porous metal sheet having a metal layer on a surface of aframework thereof a porous base material comprising a foamed sheet, apiece of nonwoven cloth or a mesh sheet or a combination of two or moreof the foamed sheet, the nonwoven cloth, and the mesh sheet layered oneon the other, by plating the porous base material and/or applying finemetal powders thereto;

applying fine metal powders linearly continuously in a stripeconfiguration to the porous metal sheet;

passing the porous metal sheet through a pair of rolls having aplurality of projections formed thereon to compress the entire finemetal powders applied thereto in a stripe configuration against theprojections to form solid metal portions,

whereby at least one lead made of solid metal is formed thereoncontinuously in a predetermined width on the porous metal sheet.

In this method, in forming solid metal portions, preferably, fine metalpowders are applied to the upper and lower surface of the porous metalsheet linearly, and then, pressed by the upper and lower projections ofa pair of upper and lower rolls so as to form the solid metal portionson the upper and lower surfaces of the porous metal sheet.

After the lead made of the solid metal is formed, the porous basematerial made of resin and the like is baked to remove from the metalportions and then, metal portions are sintered.

Fine metal powders to be applied to the entire recesses or portions tobe formed as the leads are mixed with binder to form slurry. The slurryis applied to the surface of the metal porous sheet by rotary screenmethod, roll coating method, and doctor coating method.

The following metals are used as the fine metal powders: Ni, Fe, Ag, Cu,Zn, and Fe--Cr alloy. Acrylic resin, epoxy resin, and phenol resin arepreferably used as the binder.

It is preferable to set the viscosity of the slurry to 500-25000 cps.

The amount of the slurry to be applied to the porous base material is inthe range from 300 to 1500 g/m². The width of each lead is in the rangefrom 2.0 to 20.0 mm. The thickness of each lead is in the range from0.02 mm to 0.3 mm which is smaller than the thickness of the metalporous sheet.

The solid metal portions are formed continuously on the metal-providedporous sheet in the lengthwise direction thereof by spacing them atpredetermined intervals in the widthwise direction thereof. Themetal-provided porous sheet is slitted along the solid metal portions inthe lengthwise direction thereof. In a result, a plurality of the metalporous sheet having a lead disposed at least one edge in the width wisedirection thereof are obtained.

In another aspect of the present invention, the lead-provided porousmetal sheet manufactured by the above-mentioned method is proposed. Thatis, the lead-provided porous metal sheet of the present inventioncomprises of the framework of the porous base sheet which is constitutedof a conductive metal layer formed by electroplating or fine metalpowders and leads which are made of solid metal consisting of fine metalpowders and formed in a predetermined width in the lengthwise directionof the metal-provided porous sheet.

The leads made of the solid metal portions are formed continuously onthe upper and lower surfaces of the porous metal sheet extend in thelengthwise direction thereof with predetermined intervals providedbetween them in the widthwise direction thereof. The porous metal sheetis slitted along each lead in the lengthwise direction thereof, and cutto predetermined lengths in directions perpendicular to the lengthwisedirection. Then, a plurality of the metal porous sheet having a lead onat least one edge thereof are obtained by slitting and cutting. Thelead-provided porous metal sheet is coiled, the lead is disposed alongone edge in the widthwise direction thereof.

An active substance is charged into pores of the porous metal sheetexcept the leads, and then, the porous metal sheet is cut to provide thelead-provided porous metal sheet as a strip to be used as a spiral typeelectrode plate.

According to the present invention, a porous base material such as afoamed sheet, a mesh sheet or a piece of nonwoven cloth is used to formthe metal porous sheet. While the porous base material is beingprocessed into a porous metal sheet or at the last stage of the process,the porous base material is pressed by a pair of upper and lower rollshaving projections formed thereon so as to define recesses thereonhaving pores on the surfaces thereof at a very small percentage. Then,fine metal powders are applied to the recesses. In this manner, leadsconsisting of solid metal can be manufactured very easily.

According to another method, after fine metal powders are appliedlinearly on the porous base material, portions to which the fine metalpowders have been applied are pressed by the projections of the rolls.In this manner, leads made of solid metal consisting of dense fine metalpowders can be easily formed.

As such, the present invention eliminates the need for the provision ofthe lead-forming sheet required in the conventional method.

In adjusting the position of the lead or the width thereof depending onthe type of a battery, it is only necessary to adjust the verticalpositions of the projections of the rolls and positions to which thefine metal powders are applied linearly.

Further, because the leads consisting of solid metal are integral withthe porous metal sheet, the porous metal sheet is allowed to have a highstrength.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other objects and features of the present invention willbecome clear from the following description taken in conjunction withthe preferred embodiments thereof with reference to the accompanyingdrawings throughout which like parts are designated by like referencenumerals, and in which:

FIG. 1A is a plan view showing a lead-provided porous metal sheetaccording to the present invention;

FIG. 1B is a sectional view showing the lead-provided porous metal sheetshown in FIG. 1A;

FIG. 2 is a schematic view showing a strip formed by cutting thelead-provided porous metal sheet shown in FIG. 1A to a plurality ofstrips;

FIG. 3 is a flowchart showing a method for manufacturing a lead-providedporous metal sheet according to a first embodiment of the presentinvention;

FIG. 4 is a front view showing a state in which grooves are formed bymeans of a pair of stepped rolls at step #3 of the flowchart shown inFIG. 3;

FIG. 5 is a sectional view showing a base material having the groovesformed by the process shown in FIG. 4;

FIG. 6 is a sectional view showing a state in which fine metallicpowders have been applied to the grooves shown in FIG. 5;

FIG. 7A is a schematic side view showing an apparatus for applyingslurry containing fine metallic powders to a base material;

FIG. 7B is a schematic front view showing the apparatus for applying theslurry of fine metallic powders to the base material;

FIG. 8A is a schematic side view showing another apparatus for applyingslurry of fine metallic powders to the base material;

FIG. 8B is a partly enlarged view showing the apparatus for applying theslurry of fine metallic powders to the base material;

FIGS. 9A, 9B and 9C are block diagrams showing a process ofmanufacturing a lead-provided porous metal sheet according to secondthrough fourth embodiments of the present invention;

FIGS. 10A, 10B, 10C and 10D are block diagrams showing a process ofmanufacturing a lead-provided porous metal sheet according to fifththrough eighth embodiments of the present invention;

FIG. 11 is a schematic view showing a part of the process to beperformed in the second embodiment;

FIG. 12 is a schematic view showing an apparatus for applying slurrycontaining fine metallic powders to an entire base material;

FIG. 13 is a perspective view showing a collection mechanism of a spiraltype electrode plate;

FIG. 14A is a schematic view showing a conventional method formanufacturing a lead-provided porous metal sheet; and

FIG. 14B is a schematic view showing another conventional method formanufacturing a lead-provided porous metal sheet.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Before the description of the present invention proceeds, it is to benoted that like parts are designated by like reference numeralsthroughout the accompanying drawings.

A lead-provided porous metal sheet according to a first embodiment ofthe present invention is described below with reference to FIGS. 1through 8.

FIG. 1 shows a lead-provided porous metal sheet according to the firstembodiment of the present invention. The lead-provided porous metalsheet 11 comprises a porous metal portion 14 comprising a metal foamedsheet 12 and a metal mesh sheet 13 overlaid entirely on one side of themetal foamed sheet 12; and a plurality of leads 15, composed of solidmetal, extending continuously in the lengthwise direction of thelead-provided porous metal sheet 11 and spaced at regular intervals inthe widthwise direction X thereof.

The case in which the lead-provided porous metal sheet 11 is used as thematerial of a spiral type electrode plate is described below, before themethod for manufacturing the lead-provided porous metal sheet 11 isdescribed.

First, an active substance is charged into porous metal portion 14 ofthe lead-provided porous metal sheet 11 while it is continuouslysupplied. The porous metal portion 14 are formed on the metal foamedsheet 12 and metal mesh sheet 13 overlaid on the metal foamed sheet 12and a percentage of porosity is approximately 95. Thus, during thecharging operation, the active material is charged into the pores of themetal foamed sheet 12 and the metal mesh sheet 13, whereas it is notcharged into the lead 15 because the lead 15 does not have pores formedthereon.

The lead-provided porous metal sheet 11 into which the active materialhas been charged is cut in the lengthwise direction Y of thelead-provided porous metal sheet 11 along a one-dot chain line C₁connecting the center of each lead 15 in the widthwise direction of thelead 15. Then, the lead-provided porous metal sheet 11 is cut alongone-dot chain line C₂ extending in the direction Z perpendicular to thelengthwise direction Y of the lead-provided porous metal sheet 11.Consequently, an electrode plate 16 consisting of a strip obtained bycutting the lead-provided porous metal sheet 11 is prepared, as shown inFIG. 2.

In the electrode plate 16, the sum of the width W1 of the porous metalportion 14 and 1/2×S of the width W2 of the lead 15 is set to be equalto the height of the electrode plate 16, and the lead 15 is disposed atthe upper and lower ends of the electrode plate 16 in the verticaldirection thereof.

In using the electrode plate 16 as positive and negative electrodeplates of the spiral type electrode, the positive and negative electrodeplates are spirally wound with a separator sandwiched therebetween byvarying the positions thereof vertically from each other in a smallextent, and the lead 15 is projected from the edges of the positive andnegative electrode plates in the vertical direction thereof, asdescribed previously in describing the conventional art with referenceto FIG. 13. A metallic collection terminal comprising a metallic lathplate, a metallic net plate and the like is welded to the lead 15projecting from the edges of the electrode plates, with the formerplaced on the latter.

Different from the method of collecting electric current generated inthe electrode plate by installing collection terminals at one pointthereof, the multipoint collection method allows electric current to becollected from a plurality of points of one electrode plate as describedpreviously. Accordingly, the internal pressure of the battery can bereduced and thus, the battery has a favorable discharge characteristic.

Needless to say, a plurality of collection terminals can be spot-weldedto the lead 15 at one point to utilize the multipoint collection methodas one-point collection method.

The lead-provided porous metal sheet 11 according to the firstembodiment is manufactured in accordance with a process shown by aflowchart shown in FIG. 3.

As a three-dimensional net-shape porous base material, a base material30 comprising a foamed sheet ahd a mesh sheet layered on the foamedsheet is used. At step #1, the base material 30 is unrolled.

The foamed sheet made or,polyurethane sponge is 0.5-5.0 mm in itsthickness. Favorably, the diameters of the pores range from 50 to 500 μmand more favorably, from 200 to 350 μm. Favorably, the diameters offibers of the mesh sheet are 0.01-1.0 mm and 2-mesh-200-mesh, and morefavorably, 0.05-0.1 mm and 40-mesh-120-mesh. Favorably, the porosity ofthe mesh sheet is 40-99%. The material of the mesh sheet is selectedfrom synthetic resin such as polyester, nylon, acrylic, polypropylene,polyethylene or rayon; an organic substance including natural fiber suchas cellulose or paper; and an inorganic substance such as metal, glassor carbon. The mesh sheet has a braided structure comprising braidedwarps and wefts. The fiber of the mesh-sheet is round, rectangular orflat.

At step #2, the surface of the base material 30 is treated to impartelectrical conductivity thereto, then, a porous metal material isformed.

Then, at step #3, as shown in FIG. 4, the electroplated base material 30(namely, the porous metal material 30) is passed between a pair of upperand lower stepped roils 32A and 32B each having a plurality ofprojections 31 formed on the surfaces of the rolls 32A and 32B. Theprojections 31 press the upper and lower surfaces of the electroplatedbase material 30 by spacing them at regular intervals on the surfacethereof.

The electroplated base material 30 is pressed by the projections 31 andconsequently, recessed. That is, a plurality of a pair of recesses 33Aand 33B is formed opposite to each other on the base material 30, asshown in FIG. 5.

Because the base material 30 is pressed by the projections 31, thethickness of the portion interposed between the recesses 33A and 33B isreduced from t1=0.2 mm-3.0 mm to t2=0.01 mm-0.25 mm.

As a result, the porosity of the bottom surface of the recesses 33A and33B is reduced.

At step #4, the entire surface of the base material 30 is electroplated.

The base material 30 is electroplated by the method previously proposedby the present applicant and disclosed in Japanese Laid-Open PatentPublication No. 3-241662. That is, plating liquid is allowed to collidewith the base material 30 in a plating bath in a direction substantiallyperpendicular to the base material 30, vacuum evaporation film formingmethod or electroless plating method.

In vacuum evaporation film forming method, the following metals are usedto plate the base material 30: Cu, Ni, Zn, Sn, Pd, Pb, Co, Al, Mo, Ti,Fe, SUS304, SUS430, or 30Cr. In electroless plating method, Cu, Ni, Co,Pd, Sn, or Zn is used. In electroplating method, Cu, Ni, Pd, Sn, Zn, Pb,or Fe is used.

Then, at step #5, slurry 35 formed by mixing fine metallic powders andbinder with each other is applied to the recesses 33A and 33B, as shownin FIG. 6.

Because the surface of the recesses 33A and 33B is electroplated at step#4, if the porosity of the recesses 33A and 33B is reduced to about 0%at step #4. Solid metal is formed thereon at step #5, whereas if theporosity thereof is reduced to less than 15% at step #3, the porosity isfurther reduced to 0% at step #4 and step #5.

Thus, the application of the slurry 35 to the grooves 33A and 33B allowsthe porosity thereof to be 0% and the solid metal to be completelyformed thereon.

Instead of applying the slurry 35 to the recesses 33A and 33B, it ispossible to apply binder thereto and spray fine metallic powders to thebinder. The fine metallic powders adhere to the binder.

As the fine metal powders, one of flake-shaped metal powder, ultrafinemetal powder having diameters of 0.02 μm-1.0 μm, and pulverized metalpowder having diameters of 1.0 μm-6.0 μm or a mixture of two of theabove three types of powders is used. The thickness of the flake-shapedmetal powder is 0.02 μm-1.0 μm and the longer size of the surfacethereof is 0.2 μm-10.0 μm. Preferably, the pulverized metal powders areused in combination with the flake-shaped metal powders or the ultrafinemetal powders by mixing them with each other or layering them one on theother.

For example, if pulverized metal powders having large diameters and theultrafine metal powders having small diameters are mixed with eachother, the latter penetrates into gaps between the former. Consequently,the mixed metal powders can be attached to the base material 30 at ahigh density. In addition, it is possible to overlay the flake-shapedmetal powders on the pulverized metal powders or the ultrafine metalpowders.

The following metals are used as the metal powders: Ni, Cu, Al, Ag, Fe,Zn, Sn, or Fe--Cr alloy.

The slurry 35 formed by mixing the fine metal powders and the binder isapplied to the recesses 33A and 33B by roll coating method, screencoating method, spray method or doctor coating method.

The method for attaching the fine metal powders to the electroplatedbase material 30 (namely porous metal material) is carried out by anyone of the methods proposed by the present applicant and disclosed inJapanese Laid-Open Patent Publications No. 5-229283 and 5-229284,depending on purpose.

For example, the slurry 35 composed of the binder, the flake-shapedmetal powders, and ultrafine metal powders is applied to the recesses33A and 33B of the electroplated base material 30 in a predeterminedthickness by using a screen coating apparatus shown in FIGS. 7 and 8.

In the apparatus shown in FIGS. 7A and 7B, the slurry 35 is suppliedinto a pair of coating rolls 48 so as to apply the slurry 35 to therecesses 33A and 33B through a screen constituting the peripheral wallof each coating roll 48. In the apparatus, a cylindrical peripheral wallcovered with a screen 46 made of a metal net is provided between sideplates 45 disposed at both sides of each coating roll 48. A hole 45a isdefined at the center of each side plate 45 so as to receive each end ofa slurry supply pipe 47 extending axially through the center of thecylindrical screen 46. In a pair of the coating rolls 48, slurry jettingholes 47a are formed on the slurry supply pipe 47 at regular intervals.The coating rolls 48 are vertically disposed on both sides of theelectroplated base material 30.

In the coating rolls 48, the slurry 35 is supplied to the slurry supplypipe 47 and jetted from the slurry jetting holes 47a to the recesses 33Aand 33B of the electroplated base material 30 through the screen 46.

The screen 46 allows the slurry 35 to be jetted to the recesses 33A and33B in a uniform thickness.

An apparatus-shown in FIGS. 8A and 8B is also of rotary screen type.Similarly to the apparatus shown in FIG. 7, a pair of upper and lowercoating rolls 50 is disposed on both sides of a transport path throughwhich the electroplated base material 30 travels. Similarly to thecoating rolls 48 shown in FIG. 7, the peripheral surface of each coatingroll 50 is covered with a screen 51 made of a metal net. The foam-likeslurry 35 is supplied to a squeeze 52 provided inside each coating roll50 at a pressure of two to three atmospheres from a pipe (not shown)extending axially through the center of the coating rolls 50.

The squeeze 52 has a discharge opening 52a disposed on the side on whichthe squeeze 52 is brought into contact with the electroplated basematerial 30. When the slurry 35 is supplied from the discharge opening52a to the recesses 33A and 33B through the screen 51, it contacts theatmospheric air. As a result, the foam-like slurry 35 bursts due to thedifference between the pressure thereof and that of the atmospheric air,thus returning to paste-like slurry. When the foam-like slurry 35bursts, it is supplied to the recesses 33A and 33B. Thus, a uniformthickness of slurry is formed on the recesses 33A and 33B.

As described above, the rotary screen method enables the slurry 35 to beapplied to the recesses 33A and 33B in a predetermined thickness.

It is possible to use a pair of rolls having projections to apply theslurry 35 to the recesses 33A and 33B by inserting the slurry-appliedprojections thereinto. Further, it is possible to apply the binder tothe bottom surface of the recesses 33A and 33B and spray fine metalpowders over the binder.

Then, at step #6, the electroplated base material is passed between apair of stepped rolls 32A and 32B having projections 31 formed thereonto press the projections 31 against the slurry-applied portion of theelectroplated base material 30.

Dense fine metal powders can be provided because they are pressed by theprojections 31. The metallic structure of the porous metal portion isaveraged as compression rate increases, and thus the strength thereof isincreased when they are sintered at step #8.

Then, at step #7, the electroplated base material 30 pressed at step #6is passed through a heating apparatus to heat it at a predeterminedtemperature for a predetermined period of time to burn out or remove theresin of foamed sheet and the mesh sheet from metallic layer.

At step #8, the solid metal and the porous metal portion are sintered ata predetermined temperature for a predetermined period of time bypassing it through the heating apparatus in which reducing atmospherehas been generated.

At step #9, the solid metal and the metal pore are passed between a pairof stepped rolls similar to those shown in FIG. 4 to roll them to apredetermined thickness.

At the last step #10, the lead-provided porous metal sheet 11 thusformed is wound around a roll.

As described above, the lead-provided porous metal sheet 11 shown inFIG. 1 is manufactured in the process comprising steps #1 through #10.

The method for manufacturing the lead-provided porous metal sheet 11according to the present invention is not limited to the above-describedmethods, but can be manufactured by processes of the second through theeighth embodiments shown by block diagrams of FIGS. 9(A)(B)(C) and 10(A)-(D).

In the second embodiment as shown in FIG. 9(A), after the surface of thebase material is chemically plated at step #2, the entire surface of thebase material is electroplated at step #3. Step #4 is not provided inthe second embodiment. Then, slurry consisting of fine metal powders andbinder is applied to the surface of the electroplated base material atstep #5 to form leads thereon continuously in the lengthwise directionof the electroplated base material by applying the slurry at regularintervals, namely, in a stripe configuration in the widthwise directionthereof, as shown in FIG. 11.

In the third embodiment as shown in FIG. 9(B), different from the firstembodiment, the entire surface of the base material is electroplated atstep #3, and then, recesses are formed by pressing the projections ofthe stepped rolls against the base material at step #4. Slurry isapplied to the recesses at step #5. The operations to be performed atsteps 5 through 10 are the same as those to be performed in the firstembodiment.

In the fourth embodiment as shown in FIG. 9(C), at step #2, the surfaceof the base material is not chemically plated, but slurry consisting offine metal powders and binder is applied to the entire surface of thebase material to form a conductive metal layer. The percentage of theamount of metal of the slurry to be applied to the base material in thefourth embodiment is 20% -50% of the total amount of metal to beattached thereto so as to reduce the amount of metal to be used inelectroplating the conductive metal layer at step #3. The operations tobe performed at steps 3 through 10 are the same as those to be performedin the second embodiment.

In the fifth embodiment as shown in FIG. 10(A), at step #2, slurryconsisting of fine metal powders and binder is applied to the surface ofthe base material. The percentage of the amount of metal of the slurryto be applied at step #2 to the base material in the fifth embodiment is100% of the total amount of metal to be attached thereto. Steps 3 and 4are not provided in the fifth embodiment. Slurry consisting of finemetal powders and binder is applied to the surface of the base materialcovered with metallic slurry (namely, the porous metal material) at step#5 to form leads thereon continuously in the lengthwise direction of thebase material by applying the slurry at regular intervals, namely, in astripe configuration in the widthwise direction thereof. The operationsto be performed at steps 5 through 10 are the same as those to beperformed in the second embodiment.

Similarly to the fifth embodiment, in the sixth embodiment as shown inFIG. 10(B), at step #2, slurry consisting of fine metal powders andbinder is applied to the surface of the base material. The percentage ofthe amount of metal of the slurry to be applied to the base material inthe sixth embodiment is 100% of the total amount of metal to be attachedthereto. Then, at step #3, recesses are formed by pressing theprojections of the stepped rolls against the base material covered withslurry at step #3. Step #4 is not provided in the sixth embodiment.Slurry is applied to the recesses at step #5. The operations to beperformed at steps 5 through 10 are the same as those to be performed inthe first embodiment.

Similarly to the sixth embodiment, in the seventh embodiment as shown inFIG. 10(C), at step #2, slurry consisting of fine metal powders andbinder is applied to the surface of the base material. The percentage ofthe amount of metal of the slurry to be applied to the base material inthe seventh embodiment is 100% of the total amount of metal to beattached thereto. Then, at step #3 the base material covered with slurryis heated to burn out or remove the resin of foamed sheet and the meshsheet composing the base material and the binder. Then, at step #4, thesolid metal and the porous metal portion are sintered. At step #5,recesses are formed by pressing the projections of the stepped rollsagainst the metal porous sheet at step #5. At step #6, slurry is appliedto the recesses. The operations to be performed at steps 7 through 11are the same as those to be performed in the second embodiment.

In the eighth embodiment as shown in FIG. 10(D), the operations to beperformed at steps #1 through #3 are the same as those to be performedin the second embodiment. The operations to be performed at steps #4through #12 are the same as those to be performed at steps #3 through#11 in the seventh embodiment.

As described above, in the seventh and eighth embodiments, metal isdeposited on the entire surface of the base material and then, the basematerial is heated to burn out or remove the resin of foamed sheet andthe mesh sheet composing the base material and the binder, thereby theporous metal sheet is formed. Then, recesses are formed on the porousmetal sheet by pressing the projections of the stepped rolls against thebase material. Then, slurry is applied to the recesses to form leads onthe porous metal sheet.

In the fourth through seventh embodiments, it is preferable to use rollcoating method shown in FIG. 12 in forming the porous metal sheet byapplying slurry to the base material.

In an apparatus adopting roll coating method, a pick-up roll 42 isdisposed in a liquid bath 41 reserving slurry 35, with a lower portionof the pick-up roll 42 immersed in the slurry 35, and a coating roll 43is disposed above the pick-up roll 42. A service roll 44 is positionedabove the coating roll 43, with the base material 30 sandwichedtherebetween.

In the apparatus, the slurry 35 is transferred to the coating roll 43through the pick-up roll 42. Then, the slurry 35 is applied to the basematerial 30, with the base material 30 pressed against the coating roll43 and the service roll 44.

The gap between the coating roll 43 and the service roll 44 is adjustedto adjust the application amount of the slurry to the base material 30.In the fourth through seventh embodiments, the gap is adjusted toapproximately 1/3 of the thickness of the base material 30 to impregnatethe base material 30 with the slurry 35.

In the above apparatus, the amount of the slurry 35 to be applied to thelower surface of the base material 30 is greater than that to be appliedto the upper surface thereof because the lower surface contacts thecoating roll 43 and the upper surface contacts the service roll 44. Inorder to apply the slurry 35 to the upper and lower surfaces equally, itis preferable to turn the base material 30 upside down after the slurry35 is applied to the lower surface.

In the first embodiment, the base material comprises the foamed sheetand the mesh sheet overlaid thereon, but it is possible to use amaterial comprising nonwoven cloth and a mesh sheet layered one on theother or a material comprising two mesh sheets and the nonwoven clothsandwiched therebetween. It is also possible to use only the mesh sheet,the nonwoven cloth or the foamed sheet.

Favorably, the nonwoven cloth is 0.5-5.0 mm in its thickness. Favorably,the diameters of fibers of the nonwoven cloth are 0.05-1.0 mm and morefavorably, 0.05-0.1 mm. Favorably, the porosity of the nonwoven cloth is40-99%. Similarly to the mesh sheet, the material of the nonwoven clothis selected from synthetic resin such as polyester, nylon, acrylic,polypropylene, polyethylene or rayon; organic substances such ascellulose, paper and natural fiber; and inorganic substances such asmetal, glass or carbon.

As apparent from the foregoing description, according to themanufacturing method of the present invention, the stepped rolls havingprojections formed thereon are used to form recesses on the porous metalsheet. The recesses thus formed are unporous or have pores at a verysmall percentage. Slurry comprising fine metal powders is applied to therecesses. In another method for forming leads according to the presentinvention, after fine metal powders are applied to the porous metalsheet, they are compressed by the projections of the stepped rolls. Inthis manner, leads made of unporous solid metal can be easily formed.

As such, the present invention eliminates the need for the preparationof the lead-forming sheet required in the conventional method. Thus, thelead-provided porous metal sheet can be manufactured at a low cost andin a short period of time.

The position of the lead and the width thereof can be altered by onlychanging the positions of the recesses to be formed on the porous metalsheet by the projections of the stepped rolls and the positions to whichfine metal powders are applied, depending on the type of a battery.

As described above, the lead made of continuous solid metal can beformed easily on the porous metal sheet formed by plating a foamedsheet, nonwoven cloth or a mesh sheet or a combination of at least twoof the foamed sheet, the nonwoven cloth or the mesh sheet layered one onthe other. These sheets are allowed to have porosity at more than 95%.Further, the lead can be formed in a predetermined position and width.Therefore, batteries having the lead-provided porous metal sheet used asthe electrode plates thereof are uniform in performance and further,highly efficient and provide a high-speed charge and discharge. Hencethe batteries can be reliably used. In addition, the lead-providedporous metal sheet is wide and can be successively manufactured, andthus, they are inexpensive. Furthermore, because the lead-providedporous metal sheet is coiled around a roll, it can be transported andstored easily and utilized widely.

Although the present invention has been fully described in connectionwith the preferred embodiments thereof with reference to theaccompanying drawings, it is to be noted that various changes andmodifications are apparent to those skilled in the art. Such changes andmodifications are to be understood as included within the scope of thepresent invention as defined by the appended claims unless they departtherefrom.

What is claimed is:
 1. A method of manufacturing a lead-provided porousmetal sheet comprises the steps of:plating a porous base material havinga metal layer formed on a surface of a framework of the porous basematerial, passing the porous metal material through a roll having aprojection to compress the porous metal material against the projectionand reduce or eliminate pores so as to form at least a recess; andforming solid metal portions by applying fine metal powders to therecess; whereby at least one lead made of the solid metal is formedthereon continuously in a predetermined width on the porous metalmaterial, and wherein said porous base material comprises one of asingle base material and a plurality of porous base materials layeredone on each other.
 2. The method of manufacturing a lead-provided porousmetal sheet as defined in claim 1, the fine metal powder applied intothe recess is compressed by a projection of a roll.
 3. The method ofmanufacturing a lead-provided porous metal sheet as defined in claim 2,wherein the porous base material is baked out and sintered, after thefine metal powder applied into the recess is compresses by theprojection of the roll.
 4. The method of manufacturing a lead-providedporous metal sheet as defined in claim 1, wherein the fine metal powdersto be applied so as to form as the lead are mixed with binder to formslurry, and the slurry is applied to the surface of the porous metalmaterial in a stripe configuration with a predetermined width by rotaryscreen method, roll coating method, and doctor coating method.
 5. Themethod of manufacturing a lead-provided porous metal sheet as defined inclaim 1, wherein a pair of rolls having a projection respectively areprovided at an upper and a lower surface of the porous metal material,these projections compress the upper and lower surface oppositely as toform the recess and compress the fine metal powders applied into therecess, whereby the solid metal portions are formed continuously on theupper and lower surfaces of the porous metal material.
 6. The method ofmanufacturing a lead-provided porous metal sheet as defined in claim 1,wherein the porous base material is selected from a group consisting offormed sheet, nonwoven sheet and mesh sheet.
 7. The method ofmanufacturing a lead-provided porous metal sheet as defined in claim 1,wherein the porous metal sheet is slit along each lead in a lengthwisedirection thereof, and cut to predetermined lengths in directionsperpendicular to the lengthwise directions, whereby a plurality of cutporous metal sheet having the lead disposed on at least one edge in thewidthwise direction thereof are obtained.
 8. A method of manufacturing alead-provided porous metal sheet comprises the steps of:applying finemetal powders to a porous base material having a metal layer formed on asurface of a framework of the porous base material, passing the porousmetal material through a roll having a projection to compress the porousmetal material against the projection and reduce or eliminate pores soas to form at least a recess; and forming solid metal portions byapplying fine metal powders to the recesses; whereby at least one leadmade of the solid metal is formed thereon continuously in apredetermined width on the porous metal material, and wherein saidporous base material comprises one of a single base material and aplurality of porous base materials layered one on each other.
 9. Themethod of manufacturing a lead-provided porous metal sheet as defined inclaim 8, the fine metal powder applied into the recess is compressed bya projection of a roll.
 10. The method of manufacturing a lead-providedporous metal sheet as defined in claim 9, wherein the porous basematerial is baked out and sintered, after the fine metal powder appliedinto the recess is compressed by the projection of the roll.
 11. Themethod of manufacturing a lead-provided porous metal sheet as defined inclaim 8, wherein the fine metal powders to be applied so as to form asthe lead are mixed with binder to form slurry, and the slurry is appliedto the surface of the porous metal material in a stripe configurationwith a predetermined width by rotary screen method, roll coating method,and doctor coating method.
 12. The method of manufacturing alead-provided porous metal sheet as defined in claim 8, wherein a pairof rolls having a projection respectively are provided at an upper and alower surface of the porous metal material, these projections compressthe upper and lower surface oppositely as to form recess and compressthe fine metal powders applied into the recess, whereby the solid metalportions are formed continuously on the upper and lower surfaces of theporous metal material.
 13. The method of manufacturing a lead-providedporous metal sheet as defined in claim 8, wherein the porous basematerial is selected a group consisting or formed sheet, nonwoven sheetand mesh sheet.
 14. The method of manufacturing a lead-provided porousmetal sheet as defined in claim 8, wherein the porous metal sheet isslit along each lead in a lengthwise direction thereof, and cut topredetermined lengths in directions perpendicular to the lengthwisedirections, whereby a plurality of cut porous metal sheet having thelead disposed at least one edge in the widthwise direction thereof areobtained.
 15. A method of manufacturing a lead-provided porous metalmaterial comprises the steps of: plating one porous base material havinga metal layer formed on a surface of a framework of the porous basematerial,applying fine metal powders linearly continuously in a stripeconfiguration to the porous metal material, passing the porous metalmaterial through a roll having a projection to compress the entire finepowders applied thereto in a stripe configuration to form solid metalportions, whereby at least one lead made of the solid metal is formedthereon continuously in a predetermined width on the porous metalmaterial, and wherein said porous base material comprises one of asingle base material and a plurality of porous base materials layeredone on each other.
 16. The method of manufacturing a lead-providedporous metal sheet as defined in claim 15, wherein the porous basematerial is baked out and sintered, after the fine metal powder appliedinto the recess is compressed by the projection of the roll.
 17. Themethod of manufacturing a lead-provided porous metal sheet as defined inclaim 16, wherein a pair of rolls having a projection respectively areprovided at an upper and a lower surface of the porous metal material,these projections compress the upper and lower surface oppositely as toform recess and compress the fine metal powders applied into the recess,whereby the solid metal portions are formed continuously on the upperand lower surfaces of the porous metal material.
 18. The method ofmanufacturing a lead-provided porous metal sheet as defined in claim 15,wherein the fine metal powders to be applied so as to form as the leadare mixed with binder to form slurry, and the slurry is applied to thesurface of the porous metal material in a stripe configuration with apredetermined width by rotary screen method, roll coating method, anddoctor coating method.
 19. The method of manufacturing a lead-providedporous metal sheet as defined in claim 15, wherein a pair of rollshaving a projection respectively are provided at an upper and a lowersurface of the porous metal material, these projections compress theupper and lower surface oppositely as to form recess and compress thefine metal powders applied into the recess, whereby the solid metalportions are formed continuously on the upper and lower surfaces of theporous metal material.
 20. The method of manufacturing a lead-providedporous metal sheet as defined in claim 15, wherein the porous basematerial is selected a group consisting of formed sheet, nonwoven sheetand mesh sheet.
 21. The method of manufacturing a lead-provided porousmetal sheet as defined in claim 15, wherein the porous metal sheet isslit along each lead in a lengthwise direction thereof, and cut topredetermined lengths in directions perpendicular to the lengthwisedirections, whereby a plurality of cut porous metal sheet having thelead disposed at least one edge in the widthwise direction thereof areobtained.
 22. A method of manufacturing a lead-provided porous metalmaterial comprises the steps of:applying fine metal powders to a porousbase material having a metal layer formed on a surface of a framework ofthe porous base material, applying fine metal powders linearlycontinuously in a stripe configuration to the porous metal material,passing the porous metal material through a roll having a projection tocompress the entire fine metal powders applied thereto in a stripeconfiguration to form solid metal portions, whereby at least one leadmade of the solid metal is formed thereon continuously in apredetermined width on the porous metal material, and wherein saidporous base material comprises one of a single base material and aplurality of porous base materials layered one on each other.
 23. Themethod of manufacturing a lead-provided porous metal sheet as defined inclaim 22, wherein the porous base material is baked out and sintered,after the fine metal powder applied into the recess is compressed by theprojection of the roll.
 24. The method of manufacturing a lead-providedporous metal sheet as defined in claim 23, wherein a pair of rollshaving a projection respectively are provided at an upper and a lowersurface of the porous metal material, these projections compress theupper and lower surface oppositely as to form recess and compress thefine metal powders applied into the recess, whereby the solid metalportions are formed continuously on the upper and lower surfaces of theporous metal material.
 25. The method of manufacturing a lead-providedporous metal sheet as defined in claim 22, wherein the fine metalpowders to be applied so as to form as the lead are mixed with binder toform slurry, and the slurry is applied to the surface of the porousmetal material in a stripe configuration with a predetermined with byrotary screen method, roll coating method, and doctor coating method.26. The method of manufacturing a lead-provided porous metal sheet asdefined in claim 22, wherein a pair of rolls having a projectionrespectively are provided at an upper and a lower surface of the porousmetal material, these projections compress the upper and lower surfaceoppositely as to form recess and compress the fine metal powders appliedinto the recess, whereby the solid metal portions are formedcontinuously on the upper and lower surfaces of the porous metalmaterial.
 27. The method of manufacturing a lead-provided porous metalsheet as defined in claim 22, wherein the porous base material isselected a group consisting of formed sheet, nonwoven sheet and meshsheet.
 28. The method of manufacturing a lead-provided porous metalsheet as defined in claim 22, wherein the porous metal sheet is slitalong each lead in a lengthwise direction thereof, and cut topredetermined lengths in directions perpendicular to the lengthwisedirections, whereby a plurality of cut porous metal sheet having thelead disposed at least one edge in the widthwise direction thereof areobtained.